Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer

Narayanan, Ashwin; Cao, Dennis; Frazer, Laszlo; Tayi, Alok S.; Blackburn, Anthea K.; Sue, Andrew C.-H.; Ketterson, John B.; Stoddart, J. Fraser; Stupp, Samuel I.

doi:10.1021/jacs.7b02279

Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer

Journal Article · Thu Jun 29 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b02279· OSTI ID:1821883

Narayanan, Ashwin ^[1]; Cao, Dennis ^[2]; Frazer, Laszlo ^[2]; Tayi, Alok S. ^[2]; Blackburn, Anthea K. ^[2]; Sue, Andrew C.-H. ^[2]; Ketterson, John B. ^[2]; ^[2]; ^[3]

Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States); CBES
Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)
Northwestern Univ., Chicago, IL (United States)

Ferroelectricity in organic materials remains a subject of great interest, given its potential impact as lightweight information storage media. Here we report supramolecular charge-transfer cocrystals formed by electron acceptor and donor molecules that exhibit ferroelectric behavior along two distinct crystallographic axes. The solid-state superstructure of the cocrystals reveals that a 2:1 ratio of acceptor to donor molecules assemble into nearly orthogonal mixed stacks in which the molecules are positioned for charge-transfer in face-to-face and edge-to-face orientations, held together by an extended hydrogen-bonding network. Polarization hysteresis was observed along the face-to-face and edge-to-face axes at room temperature. The noncentrosymmetric nature of the cocrystals, required to observe ferroelectric behavior, is demonstrated using second harmonic generation measurements. Furthermore, this finding suggests the possibility of designing supramolecular arrays in which organic molecules support multidimensional information storage.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-00ER45810

OSTI ID:: 1821883

Alternate ID(s):: OSTI ID: 1535012
OSTI ID: 1846799

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 27 Vol. 139; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Supramolecular Chemistry and Self-Assembly in Organic Materials Design Stupp, Samuel I.; Palmer, Liam C. Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm403028b	journal	September 2013
Design of Ferroelectric Organic Molecular Crystals with Ultrahigh Polarization Chen, Shuang; Zeng, Xiao Cheng Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja5017393	journal	April 2014
Lock-Arm Supramolecular Ordering: A Molecular Construction Set for Cocrystallizing Organic Charge Transfer Complexes Blackburn, Anthea K.; Sue, Andrew C. -H.; Shveyd, Alexander K. Journal of the American Chemical Society, Vol. 136, Issue 49 https://doi.org/10.1021/ja509442t	journal	November 2014
On the Curie temperature of poly(vinylidene fluoride) Lovinger, Andrew J.; Davis, D. D.; Cais, R. E. Macromolecules, Vol. 19, Issue 5 https://doi.org/10.1021/ma00159a036	journal	May 1986
Confinement Effects on Crystallization and Curie Transitions of Poly(vinylidene fluoride- co -trifluoroethylene) Lutkenhaus, Jodie L.; McEnnis, Kathleen; Serghei, Anatoli Macromolecules, Vol. 43, Issue 8 https://doi.org/10.1021/ma100166a	journal	March 2010
Vortex Polarization States in Nanoscale Ferroelectric Arrays Rodriguez, B. J.; Gao, X. S.; Liu, L. F. Nano Letters, Vol. 9, Issue 3 https://doi.org/10.1021/nl8036646	journal	March 2009
Unusual phase transitions in ferroelectric nanodisks and nanorods Naumov, Ivan I.; Bellaiche, L.; Fu, Huaxiang Nature, Vol. 432, Issue 7018 https://doi.org/10.1038/nature03107	journal	December 2004
Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexes Tayi, Alok S.; Shveyd, Alexander K.; Sue, Andrew C. -H. Nature, Vol. 488, Issue 7412 https://doi.org/10.1038/nature11395	journal	August 2012
Second-harmonic imaging microscopy for visualizing biomolecular arrays in cells, tissues and organisms Campagnola, Paul J.; Loew, Leslie M. Nature Biotechnology, Vol. 21, Issue 11 https://doi.org/10.1038/nbt894	journal	October 2003
Supramolecular ferroelectrics Tayi, Alok S.; Kaeser, Adrien; Matsumoto, Michio Nature Chemistry, Vol. 7, Issue 4 https://doi.org/10.1038/nchem.2206	journal	March 2015
Athermal domain-wall creep near a ferroelectric quantum critical point Kagawa, Fumitaka; Minami, Nao; Horiuchi, Sachio Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10675	journal	February 2016
Mesoscale flux-closure domain formation in single-crystal BaTiO₃ McQuaid, R. G. P.; McGilly, L. J.; Sharma, P. Nature Communications, Vol. 2, Article No. 404 https://doi.org/10.1038/ncomms1413	journal	July 2011
Above-room-temperature ferroelectricity and antiferroelectricity in benzimidazoles Horiuchi, Sachio; Kagawa, Fumitaka; Hatahara, Kensuke Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2322	journal	January 2012
Organic ferroelectrics Horiuchi, Sachio; Tokura, Yoshinori Nature Materials, Vol. 7, Issue 5, p. 357-366 https://doi.org/10.1038/nmat2137	journal	May 2008
Enhanced electric conductivity at ferroelectric vortex cores in BiFeO3 Balke, Nina; Winchester, Benjamin; Ren, Wei Nature Physics, Vol. 8, Issue 1 https://doi.org/10.1038/nphys2132	journal	November 2011
Switchable electric polarization and ferroelectric domains in a metal-organic-framework Jain, Prashant; Stroppa, Alessandro; Nabok, Dmitrii npj Quantum Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjquantmats.2016.12	journal	September 2016
Symmetry breaking in molecular ferroelectrics Shi, Ping-Ping; Tang, Yuan-Yuan; Li, Peng-Fei Chemical Society Reviews, Vol. 45, Issue 14 https://doi.org/10.1039/C5CS00308C	journal	January 2016
Bulk characterization methods for non-centrosymmetric materials: second-harmonic generation, piezoelectricity, pyroelectricity, and ferroelectricity Ok, Kang Min; Chi, Eun Ok; Halasyamani, P. Shiv Chemical Society Reviews, Vol. 35, Issue 8 https://doi.org/10.1039/b511119f	journal	January 2006
Pyroelectricity and Optical Second Harmonic Generation in Polyvinylidene Fluoride Films Bergman, J. G.; McFee, J. H.; Crane, G. R. Applied Physics Letters, Vol. 18, Issue 5 https://doi.org/10.1063/1.1653624	journal	March 1971
A Powder Technique for the Evaluation of Nonlinear Optical Materials Kurtz, S. K.; Perry, T. T. Journal of Applied Physics, Vol. 39, Issue 8 https://doi.org/10.1063/1.1656857	journal	July 1968
Depolarization fields in thin ferroelectric films Mehta, R. R.; Silverman, B. D.; Jacobs, J. T. Journal of Applied Physics, Vol. 44, Issue 8 https://doi.org/10.1063/1.1662770	journal	August 1973
Redetermination of the Structure of the Ferroelectric Crystal Guanidinium Aluminum Sulfate Hexahydrate, GASH, and its Chromium Isomorph Schein, B. J. B.; Lingafelter, E. C.; Stewart, J. M. The Journal of Chemical Physics, Vol. 47, Issue 12 https://doi.org/10.1063/1.1701777	journal	December 1967
Piezoelectricity and related properties of vinylidene fluoride and trifluoroethylene copolymers Koga, Keiko; Ohigashi, Hiroji Journal of Applied Physics, Vol. 59, Issue 6 https://doi.org/10.1063/1.336351	journal	March 1986
Structural Studies of 1:1 Quinone-Hydroquinone Complexes Desiraju, Gautam R.; Curtin, David Y.; Paul, Iain C. Molecular Crystals and Liquid Crystals, Vol. 52, Issue 1 https://doi.org/10.1080/00268947908071742	journal	April 1979
Depolarization corrections to the coercive field in thin-film ferroelectrics Dawber, M.; Chandra, P.; Littlewood, P. B. Journal of Physics: Condensed Matter, Vol. 15, Issue 24 https://doi.org/10.1088/0953-8984/15/24/106	journal	June 2003
Ferroelectrics go bananas Scott, J. F. Journal of Physics: Condensed Matter, Vol. 20, Issue 2 https://doi.org/10.1088/0953-8984/20/02/021001	journal	December 2007
Vortex ferroelectric domains Gruverman, A.; Wu, D.; Fan, H-J Journal of Physics: Condensed Matter, Vol. 20, Issue 34 https://doi.org/10.1088/0953-8984/20/34/342201	journal	August 2008
Principles and Applications of Ferroelectrics and Related Materials Lines, M. E.; Glass, A. M. https://doi.org/10.1093/acprof:oso/9780198507789.001.0001	book	February 2001
Optical Harmonic Generation in Single Crystal BaTi O 3 Miller, Robert C. Physical Review, Vol. 134, Issue 5A https://doi.org/10.1103/PhysRev.134.A1313	journal	June 1964
Phenomenological theory of optical second- and third-harmonic generation from cubic centrosymmetric crystals Sipe, J.; Moss, D.; van Driel, H. Physical Review B, Vol. 35, Issue 3 https://doi.org/10.1103/PhysRevB.35.1129	journal	January 1987
Grain-size effect on structure and phase transformations for barium titanate Frey, M. H.; Payne, D. A. Physical Review B, Vol. 54, Issue 5 https://doi.org/10.1103/PhysRevB.54.3158	journal	August 1996
Comment on “Ferroelectric Order of Parallel Bistable Hydrogen Bonds” Cai, Hong-Ling; Fu, Da-Wei; Zhang, Yi Physical Review Letters, Vol. 109, Issue 16 https://doi.org/10.1103/PhysRevLett.109.169601	journal	October 2012
Are Hydrogen-Bonded Charge Transfer Crystals Room Temperature Ferroelectrics? D’Avino, Gabriele; Verstraete, Matthieu J. Physical Review Letters, Vol. 113, Issue 23 https://doi.org/10.1103/PhysRevLett.113.237602	journal	December 2014
Discovery of a Neutral-to-Ionic Phase Transition in Organic Materials Torrance, J. B.; Vazquez, J. E.; Mayerle, J. J. Physical Review Letters, Vol. 46, Issue 4 https://doi.org/10.1103/PhysRevLett.46.253	journal	January 1981
Anomalous Nature of Neutral-to-Ionic Phase Transition in Tetrathiafulvalene-Chloranil Torrance, J. B.; Girlando, A.; Mayerle, J. J. Physical Review Letters, Vol. 47, Issue 24 https://doi.org/10.1103/PhysRevLett.47.1747	journal	December 1981
Domain-wall dynamics in organic charge-transfer compounds with one-dimensional ferroelectricity Tokura, Y.; Koshihara, S.; Iwasawa, N. Physical Review Letters, Vol. 63, Issue 21 https://doi.org/10.1103/PhysRevLett.63.2405	journal	November 1989
publCIF : software for editing, validating and formatting crystallographic information files Westrip, Simon P. Journal of Applied Crystallography, Vol. 43, Issue 4 https://doi.org/10.1107/S0021889810022120	journal	June 2010
Reliability of second-harmonic generation in crystalline powders at optical frequencies as a test of absence of centrosymmetry Coda, A.; Pandarese, F. Journal of Applied Crystallography, Vol. 9, Issue 3 https://doi.org/10.1107/S0021889876010947	journal	June 1976
Structure validation in chemical crystallography Spek, Anthony L. Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155 https://doi.org/10.1107/S090744490804362X	journal	January 2009
Second harmonic generation from the `centrosymmetric' crystals Nalla, Venkatram; Medishetty, Raghavender; Wang, Yue IUCrJ, Vol. 2, Issue 3 https://doi.org/10.1107/S2052252515002183	journal	March 2015
Applications of Modern Ferroelectrics Scott, J. F. Science, Vol. 315, Issue 5814 https://doi.org/10.1126/science.1129564	journal	February 2007
Direct Observation of Continuous Electric Dipole Rotation in Flux-Closure Domains in Ferroelectric Pb(Zr,Ti)O3 Jia, C. -L.; Urban, K. W.; Alexe, M. Science, Vol. 331, Issue 6023 https://doi.org/10.1126/science.1200605	journal	March 2011
Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal Fu, D. -W.; Cai, H. -L.; Liu, Y. Science, Vol. 339, Issue 6118 https://doi.org/10.1126/science.1229675	journal	January 2013
Ferroelectric Memories Scott, J. F.; Paz de Araujo, C. A. Science, Vol. 246, Issue 4936 https://doi.org/10.1126/science.246.4936.1400	journal	December 1989
Anomalous Valence Fluctuation Near a Ferroelectric Transition in an Organic Charge-Transfer Complex Horiuchi, Sachio; Okimoto, Yoichi; Kumai, Reiji Journal of the Physical Society of Japan, Vol. 69, Issue 5 https://doi.org/10.1143/JPSJ.69.1302	journal	May 2000
SHG from centrosymmetric supermolecular crystal Guo, Wensheng Science in China Series B, Vol. 45, Issue 3 https://doi.org/10.1360/02yb9035	journal	January 2002
Theory of optical second-harmonic generation from a sphere of centrosymmetric material: small-particle limit Dadap, Jerry I.; Shan, Jie; Heinz, Tony F. Journal of the Optical Society of America B, Vol. 21, Issue 7 https://doi.org/10.1364/JOSAB.21.001328	journal	January 2004
Second-harmonic generation as a tool for studying electronic and magnetic structures of crystals: review Fiebig, Manfred; Pavlov, Victor V.; Pisarev, Roman V. Journal of the Optical Society of America B, Vol. 22, Issue 1 https://doi.org/10.1364/JOSAB.22.000096	journal	January 2005
Second Harmonic Generation in Some Donor-Acceptor Substituted Chalcone Derivatives Patil, P. S.; Bhumannavar, V. M.; Bannur, M. S. Journal of Crystallization Process and Technology, Vol. 03, Issue 03 https://doi.org/10.4236/jcpt.2013.33018	journal	January 2013

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Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer

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